JPS63165463A - Thermosetting acrylic resin powder-coating composition - Google Patents
Thermosetting acrylic resin powder-coating compositionInfo
- Publication number
- JPS63165463A JPS63165463A JP31348086A JP31348086A JPS63165463A JP S63165463 A JPS63165463 A JP S63165463A JP 31348086 A JP31348086 A JP 31348086A JP 31348086 A JP31348086 A JP 31348086A JP S63165463 A JPS63165463 A JP S63165463A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- acrylic resin
- alkyl
- glycidyl
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 22
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 22
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 7
- 239000008199 coating composition Substances 0.000 title claims description 6
- -1 alkyl titanate compound Chemical class 0.000 claims abstract description 14
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000002075 main ingredient Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 30
- 239000011248 coating agent Substances 0.000 abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 4
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 abstract description 4
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 abstract description 2
- 235000011037 adipic acid Nutrition 0.000 abstract description 2
- 239000001361 adipic acid Substances 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 1
- QJGNSTCICFBACB-UHFFFAOYSA-N 2-octylpropanedioic acid Chemical compound CCCCCCCCC(C(O)=O)C(O)=O QJGNSTCICFBACB-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- YHGNXQAFNHCBTK-OWOJBTEDSA-N trans-3-hexenedioic acid Chemical compound OC(=O)C\C=C\CC(O)=O YHGNXQAFNHCBTK-OWOJBTEDSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は熱硬化性アクリル樹脂粉体塗料組成物に関し、
更に詳しくは低温で溶融・硬化し、しかも硬度、耐衝撃
性、耐屈曲性などの物理的強度、耐溶剤性などの化学的
性質および平滑性やりコート付着性などのすぐれた塗膜
を形成する熱硬化性アクリル樹脂粉体塗料組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting acrylic resin powder coating composition,
More specifically, it melts and hardens at low temperatures, and forms a coating film with excellent physical strength such as hardness, impact resistance, and bending resistance, chemical properties such as solvent resistance, and smoothness and adhesion to spear coats. The present invention relates to a thermosetting acrylic resin powder coating composition.
近年、粉体塗料の用途拡大はめざましく、なかでもアク
リル轡脂系粉体塗料はその優れた耐候性、耐汚染性、耐
薬品性を生かして着実に使用実績な伸ばしている。一方
、最近、省エネルギーの立場から、焼付温度の低温化の
市場要求が強まり１品質改良が急がれている。焼付温度
の低温化法として１例えばアクリル樹脂中のグリシジル
官能基を増量することが行なわれていたが、塗膜の平滑
性、リコート付着性や塗料自体の貯蔵安定性などが低下
するという欠陥が生じる。In recent years, the use of powder coatings has expanded dramatically, and acrylic resin-based powder coatings in particular have been steadily gaining use due to their excellent weather resistance, stain resistance, and chemical resistance. On the other hand, recently, from the standpoint of energy conservation, there has been an increasing market demand for lower baking temperatures, and quality improvements are urgently needed. For example, increasing the amount of glycidyl functional groups in acrylic resin has been used as a method for lowering the baking temperature, but this method has the drawback of decreasing the smoothness of the coating film, recoat adhesion, and storage stability of the coating itself. arise.
本発明者等は、熱硬化性アクリル樹脂系粉体塗料におい
て、上記のごとき欠陥を生じせしめることなく低温硬化
性を付与すべく鋭意研究を続けた結果、特定のグリシジ
ル基官能性アクリル樹脂と脂肪族二塩基酸もしくはその
無水物とを主成分とする粉体塗料に、特定のフルキルチ
タネート化合物を配合することによって上記目的が達成
できることを見出し本発明を完成するに至ったものであ
る。The inventors of the present invention have conducted extensive research in order to impart low-temperature curability to thermosetting acrylic resin powder coatings without causing the defects described above. The present invention has been completed based on the discovery that the above object can be achieved by blending a specific furkyl titanate compound into a powder coating whose main component is a group dibasic acid or its anhydride.
すなわち１本発明は、
（１）アクリル酸またはメタクリル酸のアルキルエステ
ル（但しアルキル基は炭素ａ ｔ〜１４）から選ばれた
１種以上とアクリル酸またはメタクリル酸のグリシジル
エステルから選ばれた１種以上とを主成分として共重合
させて得られるグリシジル基官能性アクリル樹脂
（２）脂肪族二塩基酸もしくはその無水物、および
（３）一般式Ｔｉ（ＯＲ）ａで表わされるアルキルチタ
ネート化合物（ただし、Ｒは炭素数が１５〜２０のアル
キル基）
を主成分とする熱硬化性アクリル樹脂粉体塗料組成物に
関する。That is, 1 the present invention provides: (1) one or more selected from alkyl esters of acrylic acid or methacrylic acid (however, the alkyl group has a carbon atom to 14 carbon atoms) and one or more selected from glycidyl esters of acrylic acid or methacrylic acid; A glycidyl group-functional acrylic resin obtained by copolymerizing the above with the main components (2) an aliphatic dibasic acid or its anhydride, and (3) an alkyl titanate compound represented by the general formula Ti(OR)a (but , R is an alkyl group having 15 to 20 carbon atoms.
本発明の特徴はグリシジル基官能性アクリル樹脂と脂肪
族二塩基酸もしくはその無水物とを主成分とする熱硬化
性粉体塗料に、さらに硬化促進剤として特定のアルキル
チタネート化合物を配合せしめるところにある。その結
果、塗膜の平滑性。The feature of the present invention is that a specific alkyl titanate compound is further blended as a curing accelerator into a thermosetting powder coating whose main components are a glycidyl group-functional acrylic resin and an aliphatic dibasic acid or its anhydride. be. As a result, the smoothness of the coating film.
リコート付着性および貯蔵安定性などを何ら低下させる
ことなく、従来のアクリル樹脂系粉体塗料の焼付温度が
一般に１８０〜１８０℃であったものを、それよりも１
０℃以上低い温度（具体的には約１５０℃以下）で塗膜
を溶融硬化することが可能となり、且つ他の塗膜性能（
例えば、硬度。The baking temperature of conventional acrylic resin powder coatings, which is generally 180 to 180℃, has been improved to 180℃ without reducing recoat adhesion or storage stability.
It becomes possible to melt and harden the coating film at a temperature lower than 0°C (specifically, about 150°C or lower), and improves other coating film performance (
For example, hardness.
耐衝撃性、耐屈曲性、耐溶剤性など）がすぐれていると
いう顕著な効果を発揮する。It exhibits remarkable effects such as excellent impact resistance, bending resistance, solvent resistance, etc.).
本発明に於いて使用されるグリシジル基官能性アクリル
樹脂はアクリル酸またはメタアクリル酸のアルキルエス
テル（但しアルキル基の炭素数は１〜１４、以下略す）
の１種または２種以上が４０重量％以上、アクリル酸ま
たはメタアクリル酸のグリシジルエステルの１種または
２種以上が５〜６０重量％の共重合割合の共重合体であ
って更に必要に応じスチレン、ビニルトルエン、アクリ
ロニトリル、アクリル酸又はメタアクリル酸のヒドロキ
シルアルキルエステル、酢酸ビニルから選ばれた１種ま
たは２種以上の単量体を５５重量％以下共重合せしめる
ことが出来る。アクリル酸またはメタアクリル酸のアル
キルエステルが４０重量％より少ない場合は塗膜の耐候
性および耐汚染性が低下することがある。またアクリル
酸のグリシジルエステルの共重合比があまりに大きくな
れば高価になるばかりで物性の点に於いてより以上の効
果はあまり期待出来ず、また５重量％に達しない場合は
架橋性が低下し熱硬化性アクリル樹脂の特性が損なわれ
てしまうおそれがある。The glycidyl group-functional acrylic resin used in the present invention is an alkyl ester of acrylic acid or methacrylic acid (however, the number of carbon atoms in the alkyl group is 1 to 14, hereinafter omitted).
A copolymer with a copolymerization ratio of 40% by weight or more of one or more of the following, and 5 to 60% by weight of one or more glycidyl esters of acrylic acid or methacrylic acid, and further as necessary. Up to 55% by weight of one or more monomers selected from styrene, vinyltoluene, acrylonitrile, hydroxyalkyl esters of acrylic acid or methacrylic acid, and vinyl acetate can be copolymerized. If the amount of alkyl ester of acrylic acid or methacrylic acid is less than 40% by weight, the weather resistance and stain resistance of the coating film may decrease. Furthermore, if the copolymerization ratio of glycidyl ester of acrylic acid is too large, it will only become expensive and no further effects can be expected in terms of physical properties, and if it does not reach 5% by weight, the crosslinking property will decrease. There is a risk that the properties of the thermosetting acrylic resin will be impaired.
本発明に於いては硬化剤として脂肪族二塩基酸およびそ
の無水物を使用する。ここに脂肪族二塩基酸としては一
般式ＨＯＯＣ−Ｒ−ＣＯＯＨにおいて、Ｒの炭素数が４
〜１４である飽和あるいは不飽和脂肪酸ならびにそれら
のハロゲン付加物が包含される。好ましい例としてはア
ジピン酸、ピメリン酸、セバシン酸、アゼライン酸、ノ
ナンジカルボン酸、デカンジカルボン酸、ウンデカンジ
カルボン酸、ジヒドロムコン酸、ムコン酸などがあげら
れる。In the present invention, aliphatic dibasic acids and their anhydrides are used as curing agents. Here, as the aliphatic dibasic acid, in the general formula HOOC-R-COOH, R has 4 carbon atoms.
-14 saturated or unsaturated fatty acids and their halogen adducts. Preferred examples include adipic acid, pimelic acid, sebacic acid, azelaic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dihydromuconic acid, muconic acid, and the like.
グリシジル基官能性アクリル樹脂と上記硬化剤との混合
比（重量）は好ましくはアクリル樹脂中のグリシジル基
１当量に対して脂肪族二塩基酸の分子中に含有されるカ
ルボキシ基として０．５〜２．０当量とするのが良く、
通常グリシジル基官能性アクリル樹脂７０〜９５重量％
に対し硬化剤５〜３０重量％とすれば良い。The mixing ratio (weight) of the glycidyl group-functional acrylic resin and the curing agent is preferably 0.5 to 0.5 to 1 equivalent of the glycidyl group in the acrylic resin as carboxy groups contained in the molecule of the aliphatic dibasic acid. It is better to set it as 2.0 equivalent,
Normally glycidyl group functional acrylic resin 70-95% by weight
The amount of curing agent may be 5 to 30% by weight.
本発明において用いるアルキルチタネート化合物は、一
般式Ｔｉ （ＯＲ）４ （式中Ｒは炭素数１５〜２０
のアルキル基である）で示される化合物であり、具体例
としてはテトラペンタデシルチタネート（Ｃ１５） 、
テトラヘキサデシルチタネート（Ｃ１６）、テトラヘプ
タデシルチタネー）（Ｃ１７）、テトラノニルデシルチ
タネート（Ｃ１９）等が挙げられ、このうち、前３者が
特に好ましい、上記一般式中のＨについて、炭素数が１
４以下になると該化合物が液状となり貯蔵安定性や耐ブ
ロッキング性が低下し、一方、２１より大きくなると低
温硬化性が十分でなく、本発明の目的が達せられない。The alkyl titanate compound used in the present invention has the general formula Ti (OR)4 (wherein R has 15 to 20 carbon atoms).
is an alkyl group), and specific examples include tetrapentadecyl titanate (C15),
Examples include tetrahexadecyl titanate (C16), tetraheptadecyl titanate (C17), and tetranonyldecyl titanate (C19), among which the former three are particularly preferred. is 1
If it is less than 4, the compound becomes liquid and the storage stability and anti-blocking properties are reduced, while if it is greater than 21, the low temperature curability is insufficient and the object of the present invention cannot be achieved.
これらのフルキルチタネート化合物が水酸基、チオ基も
しくはアミノ基を有する重合体の架橋剤として有用なこ
とはすでに知られているが、グリシジル基含有アクリル
樹脂と脂肪族二塩基酸とからなる粉体塗料の架橋硬化反
応を低温で促進すること、かつ架橋反応によりアルキル
チタネート化合物から副生ずる高級アルコールも融点が
４０℃以上のものであるため、その硬化塗膜の平滑性な
らびにリコート付着性が良好となり、しかも塗料自体の
ブロッキング性などがすぐれていることなどはおどろく
べき効果である。It is already known that these furkyl titanate compounds are useful as crosslinking agents for polymers having hydroxyl groups, thio groups, or amino groups, but powder coatings made of glycidyl group-containing acrylic resins and aliphatic dibasic acids. By accelerating the crosslinking and curing reaction at low temperatures, and because the higher alcohol by-produced from the alkyl titanate compound by the crosslinking reaction also has a melting point of 40°C or higher, the smoothness and recoat adhesion of the cured coating film are improved, What's more, the paint itself has excellent blocking properties, which is a surprising effect.
本発明において、アルキルチタネート化合物の配合量は
、グリシジル基官能性アクーリル樹脂と脂肪族二項′基
酸もしくはその無水物との総量１００重量部に対して、
０．２〜５重量部、特に０．３〜２．５重量部の範囲が
好ましく、０．２重量部より少ないと硬化促進の効果が
十分でなく、一方５重量部より多くなると塗膜の耐水性
を損なう傾向がある。In the present invention, the blending amount of the alkyl titanate compound is as follows:
The range of 0.2 to 5 parts by weight, particularly 0.3 to 2.5 parts by weight, is preferable; if it is less than 0.2 parts by weight, the effect of accelerating curing will not be sufficient, while if it is more than 5 parts by weight, the coating film will deteriorate. It tends to impair water resistance.
本発明粉体塗料組成物を製造するに際しては、上記各成
分に必要に応じて顔料、充填材、タレ防止剤を混合し、
８０〜１３０℃程度で充分に加熱混練し、これを冷却後
粉砕する。溶融混線装置としては加熱ロール、加熱ニー
グー、エクストルーダーなどが用いられる。また粉体化
はこれら組成物を揮発性溶剤に溶解し熱い空気中に噴霧
して粉体にするいわゆる噴霧乾燥法等も適用できる。When producing the powder coating composition of the present invention, pigments, fillers, and anti-sagging agents are mixed as necessary with each of the above components,
The mixture is sufficiently heated and kneaded at about 80 to 130°C, cooled, and then pulverized. As the melting cross-wire device, a heating roll, a heating knee goo, an extruder, etc. are used. Further, for powdering, a so-called spray drying method or the like can be applied, in which these compositions are dissolved in a volatile solvent and sprayed into hot air to form a powder.
本発明に係る粉体塗料は貯蔵安定性がすぐれており、粉
末静電塗装法、流動浸漬法などによって被塗物に塗布す
ることができる。而してその硬化条件は従来の溶剤形態
硬化アクリル樹脂塗料と同程度の１４０〜１５０℃の低
温で良い、しかも得られる塗膜は平滑性、鮮映性等の外
観、硬度、耐衝撃性、リコート付着性、耐屈曲性等の物
理的強度、並びに耐溶剤性、耐汚染性、耐水性、耐食性
等の緒特性に於いて優れた性能をもっている。The powder coating according to the present invention has excellent storage stability and can be applied to objects to be coated by electrostatic powder coating, fluidized dipping, or the like. The curing conditions can be as low as 140 to 150°C, which is the same as that of conventional solvent-cured acrylic resin paints, and the resulting coating film has excellent appearance properties such as smoothness and sharpness, hardness, impact resistance, and It has excellent physical strength such as recoat adhesion and bending resistance, as well as other properties such as solvent resistance, stain resistance, water resistance, and corrosion resistance.
以下実施例を示して本発明を具体的に説明する。尚下記
実施例に於いて部または％とあるは特に説明しないかぎ
り重量部または重量％を示す。The present invention will be specifically explained below with reference to Examples. In the following examples, parts or % refer to parts by weight or % unless otherwise specified.
実施例１〜５、比較例１〜６
メタクリル酸メチル２５部、アクリル醸ブチル２０部、
メタクリル酸グリシジル３０部、メタクリル酸ヒドロキ
シエチル５部およびスチレン２０部から粒子状グリシジ
ル基官能性アクリル樹脂を得た。このアクリル樹脂８５
部、ドデカンニ酸１５部、後記第１表に記載した所定量
の各種アルキルチタネート化合物、チタン白（ルチル形
）３０部および塗面調整剤（流れ止剤およびはじき防止
剤）１部を室温で約３〜１０分トライブレンドしたのち
、加熱エクストルーダーを用いて溶融混練した。ついで
冷却後粉砕機をもちいて粒径２０〜１００ｊＬ程度の粉
体塗料組成物を得た。得られた粉体塗料を静電粉体塗装
法により燐酸亜鉛系化成処理鋼板（厚さ０．８ｍ■）に
粉体塗装した後、熱風式乾燥機中で１５０℃の温度で２
０分間焼付けた（膜厚的７０ＪＬ）、この鋼板の塗膜性
能試験を行なった。Examples 1 to 5, Comparative Examples 1 to 6 25 parts of methyl methacrylate, 20 parts of butyl acrylate,
A particulate glycidyl group-functional acrylic resin was obtained from 30 parts of glycidyl methacrylate, 5 parts of hydroxyethyl methacrylate, and 20 parts of styrene. This acrylic resin 85
15 parts of dodecanoic acid, predetermined amounts of various alkyl titanate compounds listed in Table 1 below, 30 parts of titanium white (rutile type), and 1 part of a coating surface conditioner (anti-flow agent and anti-repellent agent) at room temperature. After tri-blending for 3 to 10 minutes, the mixture was melt-kneaded using a heating extruder. After cooling, a pulverizer was used to obtain a powder coating composition having a particle size of about 20 to 100 jL. The obtained powder coating was powder coated on a zinc phosphate chemically treated steel plate (thickness 0.8 m) using an electrostatic powder coating method, and then heated in a hot air dryer at a temperature of 150°C for 2 hours.
A coating film performance test was conducted on this steel plate which was baked for 0 minutes (film thickness: 70 JL).
比較例として、上記実施例１において用いたアルキルチ
タネート化合物に代えて、低級アルキル基のテトラブチ
ルチタネート及びアルキル基の一部がキレート形成基に
置換したチタニウムジブチルアセチルアセトネートを用
いた場合、さらにアルキルチタネート化合物無添加の場
合について試験した。これらの試験結果を第１表に併記
した。As a comparative example, when tetrabutyl titanate having a lower alkyl group and titanium dibutylacetylacetonate having a part of the alkyl group substituted with a chelate forming group were used in place of the alkyl titanate compound used in Example 1, further alkyl A test was conducted without the addition of a titanate compound. These test results are also listed in Table 1.
第１表において、
本１ ゲル化時間−
１５０℃に加熱されたホットプレート上に試料（粉体塗
料）を約１００ｍｇのせ、試料が溶融した時から流動性
がなくなるまでの時間を示す、比較例５は１６０℃・２
０分、比較例６は１８０℃Φ２０分で行なった。In Table 1, Gelation time - Comparative example showing the time from when the sample (powder paint) is placed on a hot plate heated to 150°C and the sample melts until it loses fluidity. 5 is 160℃・2
Comparative Example 6 was conducted at 180° C. for 20 minutes.
本２ ゲル分率
１５０℃・２０分で焼付けられた塗膜を、アセトンを溶
媒としたソックスレー抽出試験器に８時間かけ、不溶部
分の重量分率をゲル分率とした。比較例５は１６０℃・
２０分、比較例６は１８０℃・２０分で焼付けた。Book 2 Gel Fraction The coating film baked at 150° C. for 20 minutes was subjected to a Soxhlet extraction tester using acetone as a solvent for 8 hours, and the weight fraction of the insoluble portion was defined as the gel fraction. Comparative example 5 is 160℃・
Comparative Example 6 was baked at 180° C. for 20 minutes.
よ３ 貯蔵安定性
試料の粉体塗料を４０℃で１０日間貯蔵後のブロッキン
グ状態及びそれを静電塗装し焼付けた塗面の平滑性、ツ
ヤ等を貯蔵前のものと比較した。3.Storage Stability The blocking state of the sample powder coating after storage at 40°C for 10 days and the smoothness, gloss, etc. of the coated surface after electrostatic coating and baking were compared with those before storage.
０：全く異常なし。0: No abnormality at all.
Ｘニブロッキング性および塗膜の平滑性などが著しく低
下。X Ni-blocking properties and coating film smoothness are significantly reduced.
本４ 塗面平滑性：肉眼観察
本５ エリクセン値
塗板を恒温恒湿室（２０℃、７５％）の中に１時間置い
たのちエリクセン試験器に塗膜を外側に向けて取付け、
約１０ｍｍの曲率半径をもったポンチを試験板の裏面か
ら規定の距離だけ、毎秒的０．１ｍｓの速さでできるだ
け速さにむらがないように押出す、突出した部分の塗膜
にワレ、ハガレがあるかどうかを押出した直後に肉眼で
見て調べ、塗膜に異状がないときの最大ｆｆｉ履数で表
わした。Book 4 Painted surface smoothness: Visual observation Book 5 Erichsen value After placing the coated plate in a constant temperature and humidity chamber (20°C, 75%) for 1 hour, attach it to an Erichsen tester with the coating facing outward.
A punch with a radius of curvature of approximately 10 mm is pushed out a specified distance from the back of the test plate at a speed of 0.1 ms per second with as much uniformity as possible. The presence of peeling was visually inspected immediately after extrusion and expressed as the maximum ffi number when there was no abnormality in the coating film.
零〇 耐衝撃性
デュポン式衝撃試験器（撃芯局インチ・荷重５００ ｇ
）で塗面にワレ、ハガレを生じない最高の落下圧１！Ｉ
Ｉ （Ｃ腸）を示す。0〇 Impact resistance DuPont type impact tester (striking center inch, load 500 g
) with the highest falling pressure 1 that does not cause cracking or peeling on the painted surface! I
I (C intestine) is shown.
零７ 耐屈曲性
ＪＩＳ Ｋ５４００．曲率半径 ５ｍｍ零８ 耐溶剤
性
キジロール中にガーゼを浸し、該ガーゼを引きあげたの
ち、該ガーゼでもって塗面を往復してつよくこすり、塗
面状態を判定した（こする回数１００回）。Zero 7 Flexibility JIS K5400. Radius of curvature: 5 mm Zero 8 Gauze was immersed in solvent-resistant Kijiroll, the gauze was pulled up, and the coated surface was vigorously rubbed back and forth with the gauze to determine the condition of the coated surface (100 times of rubbing).
本９ リコート付着性
１５０℃・２０分焼付けた塗膜をさらに同温度で６０分
オーバーベークした後、同一塗料をリコートし、同一条
件で焼付けてから、２ｍｍ巾１０ＸＩＯのゴバン目カッ
トを入れ、セロテープにより付着性を試験した。剥離が
認められない場合はｔｏｏ／１００、全て剥離の場合は
０／１００で表わした。Book 9 Recoat Adhesion The coating film baked at 150°C for 20 minutes was further overbaked at the same temperature for 60 minutes, then the same paint was recoated and baked under the same conditions, and then a 2mm wide 10XIO goblin cut was made and cellophane tape was applied. The adhesion was tested by When no peeling was observed, it was expressed as too/100, and when all peeling was observed, it was expressed as 0/100.
なお、比較例５は１６０°Ｃ・２０分、比較例６は１８
０℃１１２０分焼付け、それぞれ同温度で６０分オーバ
ーベークし、さらに同一塗料をリコートシ１次いで同条
件で焼付けたものについて試験した。In addition, Comparative Example 5 was heated at 160°C for 20 minutes, and Comparative Example 6 was heated at 180°C for 20 minutes.
The samples were baked at 0° C. for 1120 minutes, overbaked at the same temperature for 60 minutes, and then recoated with the same paint and then baked under the same conditions.
Claims (3)
ル（但しアルキル基は炭素数１〜 １４）から選ばれた１種以上とアクリル酸またはメタク
リル酸のグリシジルエステルから選ばれた１種以上とを
主成分として共重合させて得られるグリシジル基官能性
アクリル 樹脂(1) The main ingredients are one or more selected from alkyl esters of acrylic acid or methacrylic acid (however, the alkyl group has 1 to 14 carbon atoms) and one or more selected from glycidyl esters of acrylic acid or methacrylic acid. Glycidyl group-functional acrylic resin obtained by copolymerization
タネート化合物（ただし、Ｒは炭素数が１５〜２０のア
ルキル基） を主成分とする熱硬化性アクリル樹脂粉体塗料組成物。(3) A thermosetting acrylic resin powder coating composition containing as a main component an alkyl titanate compound represented by the general formula Ti(OR)_4 (wherein R is an alkyl group having 15 to 20 carbon atoms).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31348086A JPS63165463A (en) | 1986-12-26 | 1986-12-26 | Thermosetting acrylic resin powder-coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31348086A JPS63165463A (en) | 1986-12-26 | 1986-12-26 | Thermosetting acrylic resin powder-coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63165463A true JPS63165463A (en) | 1988-07-08 |
Family
ID=18041811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31348086A Pending JPS63165463A (en) | 1986-12-26 | 1986-12-26 | Thermosetting acrylic resin powder-coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63165463A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0696622A2 (en) | 1994-08-11 | 1996-02-14 | MITSUI TOATSU CHEMICALS, Inc. | Thermosetting powder paint, coating method using said paint, and article coated with said paint |
| EP0750023A1 (en) | 1995-06-21 | 1996-12-27 | Mitsui Toatsu Chemicals, Incorporated | Polymer networks and powder paint for obtaining these |
| US5719212A (en) * | 1995-11-09 | 1998-02-17 | Nippon Paint Co., Ltd. | Powder coating composition of epoxy-containing acrylic, polycarboxylic acid and antioxidant |
-
1986
- 1986-12-26 JP JP31348086A patent/JPS63165463A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0696622A2 (en) | 1994-08-11 | 1996-02-14 | MITSUI TOATSU CHEMICALS, Inc. | Thermosetting powder paint, coating method using said paint, and article coated with said paint |
| US5728790A (en) * | 1994-08-11 | 1998-03-17 | Mitsui Toatsu Chemicals, Inc | Thermosetting powder paint, coating method using said paint, and article coated with said paint |
| EP0750023A1 (en) | 1995-06-21 | 1996-12-27 | Mitsui Toatsu Chemicals, Incorporated | Polymer networks and powder paint for obtaining these |
| US5719212A (en) * | 1995-11-09 | 1998-02-17 | Nippon Paint Co., Ltd. | Powder coating composition of epoxy-containing acrylic, polycarboxylic acid and antioxidant |
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